Buffered antiperspirant compositions



nited BUFFEREDANTIPERSPIRANT COMPUSITIONS NoD'rawmg'. Application April 30, 1954, Serial-N0. 426,932

Claims. (Cl. 167-90) Thisv invention relates. to anti-perspirant compositions.

Moreparticularly, this, invention relatesito highly effective ganti perspirant compositions which are non-irritating to the skin and non-corrosive to textiles;

Cosmetic preparations which have a. perspiration inhibitingor retardingeifect are well known; Many. chem-- ical. compounds capable of preventing} or retarding. the exudationqof perspiration havebeen usedior: suggestedv'for. use\in.-suc h: compositions; Among; these may. be; men tioned. tartaric-acid, ben'zoie acid, chromic.acid;.borie acid, SflltSvOfSQllCYCllC: acid, and various salts:ofizinc, iron andaluminum. The aluminum-saltsof strongeacids; and especially the chloride. and sulphate, are normally-comb sidered to be the most efficacious and findi the -mostiwidee spread use. More recently, various derivatives of Zirconiurn have-been suggested for anti-perspirant applica tions and in many respects are superior to the corresponding aluminum salts";

M any-of the aforementioned comp'ou nds however, exhibit characteristics which detract from theifvalwe as anti-perspirants and which militate against-their extended. use. For. example, chromic acid is-relati-vely-"toxic; tartaric acid boric acid, benzoic acid andthe salts-"of -salicylic acid are relatively ineflicient; the Zine-saltsare "irritating to. theskin. and. the ironsaltstend to discolor fabrics. Also, the aluminum andi-zirconium=-. salts which' are the most etfectiveantbperspirants (usually the salts of 'strong. acids). have the. disadvantage of forming strongly acid solutions. and. thushthe-useofthese materials in antiperspirant preparationsmay result in irritation to the skin. andwdamage to..c1othing. 1 Moreover, the-use of the saltsof weak acidscfiers no solution to this problemsincea such compounds are relatively ineifective in inhibiting the flow of" perspiration. In general, decreasing; acidity of the anti-perspirant compounds is accompanied-(by. decreasing anti-perspirant 'efficacy.

I It isan-objectofthis invention to provide a composition which-is-highly'effective'ininhibiting'or retarding the exudation of'perspiration'.

Afu-rther-objectof the inventioniis to 'provide'a composition whichis highly effective in inhibiting, or retard-- ing the exudation of'perspiration' and yet which is nonirritating tothe skin and non-corrosive toj textiles,

A still--further-objectis the provision of an anti-penspirant'compositioncontaininga zirconium or hafnium salt of a strong monobasic mineral acid as an essential aetive4 ingredient.

' An additional objectis the provision-of ahighly eifective, non-irritating, and nomcorrosive, anti=perspir-ant composition which may be easily applied in liquid,v semi liquid. or other forms.

Other objects Will be apparent from the following de tailed description.

I have found that the disadvantages associated with;

prior art compositions may be overcome andathe-objects tates Patent- 6 by weight on an anhydrous basis.

2,814,585 Patented Nov. 26, 19 57 of thev invention :may; be realized by; providing an 1 antiperspirant composition, comprising in combination an aqueous solution of a zirconium-or hafnium salt of strong, monobasic mineral acid, abasic aluminum compoundand. an amino acid in.;which--the= number ofjamin'o groupsis; equal :to the; number: of carboxyl gI'OHPS iH thef-fmQIeC1lIeL, For convenience,- these particular amino acids willtbe'; referred to herein as neutral amino acids.

As mentionedt hereinbefore, various zirconium-deriva-x tives have been suggested as anti-perspirantagentsr The most -.eflicacious of these are the salts of thestrong acids, andtheseform such,-strongly.acid solutions that there. is; danger: in their use; Ingeneral, it'has been recognized. that most: compounds; of zirconium, if soluble in water, are relatively highly, acid and cannot therefore safely be-usedalone inrcontact'with the skin.

I h avefound, however. that the aqueous solutions of zirconium salts,,and hafnium salts, of strong monobasic: mineral acids may be rendered usable by treating them with:certain basic,- aluminum compounds and the above mentioned amino acids. The basic aluminum compoundsand the amino. acidsact as bufiering agents to bring. the pHoh-theQsolution.ofthezirconium or hafnium salt to a' value whi ch., enders it safe foranti-perspirant usage. For example, amunbutfered, solution of zirconyl chloride,.althoughwvery elfectiveas. an anti-perspirant, has a pH of abouti0l8.andtisithereforeunfit for general anti-perspirant use; When bulferedwith abasic aluminum compound, and; amino acidin accordance with my-invention, how. ever, the solutionpH. may; be readily brought into the, rangefromaboutfif to. about 5 with substantially no loss; in,the,antiperspiranteffectiveness. This retention of anti-. perspirant"effectiveness in buffered solutionsis totally; unexpected since experience withthe various aluminurnsalts; commonly used asanti-perspirants has shown decreased. eiiicacy with buffering.v 1

Moreoyenthe, buffered. compositions. ofmy invention are much superior in anti-perspirant; effectiveness when, :comparedwithfthe aluminum compoundspreviously con-. sideredthe most effective, such as, for example, aluminum chloride or aluminum chlorhydroxide.

The zirconium. and; hafnium compounds. which have been. found" operative, for the purposes of my, invention are the chlorides, bromides, iodides. and nitrates. The zirconium and hafnium salts naInQd above are very reactive when contacted with Water andjrapidly hydrolyze to' theoxy salt' form; Thus, since thecompositions of my invention contain appreciable amounts of water, any of theaforementionedzirconium or'hafnium salts will probablybe 'pres'ent in the oxy form:

ThebasicJaluminumcompounds with which the above hafniumandzirconiumsalts arecombin'ed' have the gen eralr empirical formula Al21(OH sonXa where X is a monovalent; acid anion: of the group 61*, B1", 1- and N03 and: n has an; average value from about 0:8; to about 2. I'havefound that; the aluminum chlorhyd'roxide complex of the! formula A12(-GH)5;C1VXI'1I2O where x is about- 2 finds;- ready. application in the practice of my- .invention although. any basic aluminum compoundwithin the above defined limits gives satisfactory results.

It. is. to be appreciated that these. basic aluminum compounds in themselves have anti-perspirant properties.

In the compositions of my invention, the concentration of the anti-perspirant constituents, namely, the zirconium or hafnium salt: plus the basic aluminum salt, may vary from about 5% to about by weight, on an anhydrous basis. As a practical matter however, I prefer that this concentration be" in the range from about 10% to 30% s amens V Since, as pointed out above, the basic aluminum compounds have anti-perspirant properties, the ratio of the aluminum salt to the zirconium or hafnium salt is theoretically unlimited. In order that the objects of my invention may be achieved, however, I have found that this ratio must be controlled within certain limits. Thus,

if the weight of aluminum compound is appreciably greater than the weight of the zirconium or hafnium salt the anti-perspirant properties of the combination is -'reduced, and if the weight of the aluminum compound is much less than the weight of the zirconium or hafnium salts the desired buffering of the solution of zirconium or hafnium salt is not achieved. The optimum anti-perspirant activity and buffering efiect may be realized if the atomic ratio of aluminum to zirconium or hafnium in the composition is in the range from about 3.5:1 to 1.5 :1. With a mixture of zirconyl chloride octahydrate (ZrOCl2-8H2O) and aluminum chlorhydroxide complex (Al2(OH)sCl-2H2O), for example, the zirconium salt should preferably comprise from about 50 to 60% by weight of the mixture of the two and the aluminum compound from about 50 to 40% by weight, all weights being on a hydrated salt basis. Expressed on an anhydrous salt basis, the zirconium salt should preferably comprise from about 40 to 50% by weight of the mixture of the two and the aluminum compound from about 60 to 50% by weight.

Although, theoretically, any neutral amino acid, as hereinbefore defined, may be used to accomplish the objects of my invention, it is to be appreciated that as a practical matter only those neutral amino acids which are sufficiently soluble in aqueous solution are usable.

Among the neutral amino acids which I have found operative for the purposes of my invention are glycine, dl-tryptophane, dl-fl-phenyl-alanine, dl-valine, dlmethionine, and ,B-alanine. Sufficient neutral amino acid is added in the preparation of the compositions of my invention so that the concentration of neutral amino acid in the final composition is at least about 1%, on an anhydrous basis, and sufiicient to prevent gelling of the composition. If amounts of amino acid less than 1% by weight are used, the solution of the zirconium or hafnium salt plus the aluminum compound tend to gel within a very short time (1 to 2 weeks) and therefore, as a practical matter, less than about 1% amino acid is not desirable.

The maximum amount of neutral amino acid that may be added in preparing the compositions of my invention is limited only by practical and/or economic considera tions. Thus, I have found that high concentrations of the amino acids in my anti-perspirant compositions have a deleterious effect upon the anti-perspirant eflicacy of the composition. For example, when an anti-perspirant solution containing about 15% anti-perspirant salts (zirconyl chloride plus aluminum chlorhydroxide) and 12% glycine was tested for anti-perspirant eflicacy according to the hereinafter described test, the average reduction in sweating on fifteen subjects was found to be 63.1%. With an anti-perspirant solution containing the same amount of anti-perspirant salts (again zirconyl chloride and aluminum chlorhydroxide) but only 2.5% glycine on the other hand, the average percent reduction in sweating obtained with twelve subjects was 75.2%. Moreover, anti-perspirant preparations containing such large amounts of amino acids are not economically attractive from a marketing standpoint. For practical reasons therefore, I prefer to keep the concentration of the neutral amino acid within the range from about 1% to about 5% by weight of the anti-perspirant preparation, on an anhydrous basis. It is to be understood of course that in all instances sufiicient amounts of amino acid must be present to prevent gelation of the anti-perspirant preparation.

Prevention of gelling of the anti-perspirant preparations is extremely important since gels have been found to have such extremely limited anti-perspirant properties as to be considered useless from a practical standpoint.

I have also found that the neutral amino acids alone without any basic aluminum compound being present, will buffer a zirconyl chloride solution for example. The quantity of amino acid necessary to raise the pH of the zirconyl chloride solution to a level which is considered safe from the standpoint of skin irritation and corrosion of textiles is however prohibitively large when compared with that necessary when a basic aluminum salt is also present. For example, a 12% solution of zirconyl chloride octahydrate required 16% glycine to provide a solution pH of 3.75. Also, the anti-perspirant efiicacy of such compositions, i. e. those buffered solely with a neutral amino acid, is rather poor when compared with those compositions buffered with an amino acid and a basic aluminum salt, and is, in fact, poorer than the efficacy displayed by the well-known aluminum chloride antiperspirants. Consequently, it is not considered that those zirconium or hafnium containing anti-perspirant compositions buffered with a neutral amino acid alone fall within the scope of the present invention.

The anti-perspirant composition of my invention may be formulated into cosmetic preparations which are in liquid, semi-liquid or other forms, the water in the cosmetic preparation comprising from about 25% to by weight thereof. Representative formulas for a cream type, a lotion type and a liquid anti-perspirant utilizing zirconyl chloride octahydrate and aluminum chlorhydroxide complex as the active anti-perspirant constituents are set forth below.

, Cream: Parts by weight Zirconyl chloride (ZrOCl -8H O) 9.0 Aluminum chlorhydroxide complex (Al2(OH)5Cl'2H20) 8.0 Gly 3.0 Tegacid (glyceryl monostearate plus 5% sapamine 12.0 Spermaceti w 3.5 Cetyl alcnhnl 1,0 Glycerin 3.0 Atlas G-2152 (polyoxy alkylene stearate) 0.6 Atlas 6-2160 (polyoxy alkylene propylene glycol monostearate) 0.6 Ethanol 8.0 Water 5 1.3 Perl-um: (1.8.

Lotion: Parts by weight Zirconyl chloride (ZIOC12'8H20) 8.0 Aluminum chlorhydroxide complex (A12(OH)5C1'2H20) 7.0 Gly 4.0 Veeg 3.5 Fthanol 5,0 Water 63.5 Light mineral oil 6.0 Stearyl alcohol 1.0 Atlas G-2l5 1.0 Atlas G-2160 1.0 Perfume q s.

Liquid:

Zirconyl chloride (ZIOC1z-8H2O) 9.0 Aluminum chlorhydoxide complex (A12(OH)5C1'2H2O) 7.0 Glycin 5,0 Fthannl 30.0 Water 4&0 Triton X-400 (stearyl dimethyl benzyl ammonium chloride) 1.0

Perfume It is to be understood that i he above compositions the r ients. o he han. he ircon m and alum salts and glycine have been added, not for their antiperspirant characteristics, but to obtain a product having properties which are desirable from a purely cosmetic aspect. Also, if desired, various bacteriostatic, germicidal and/or. deodorizing agents may be added in the preparation of. these anti-perspirant cosmetic preparations. Typical of such additives are hexachlorophene (2,2'-dihydroxy-3,5,6-3 ,5,6-hexachlorodiphenyl' methme) or the quaternary ammonium salts such as Hyamine 1622 (para diisobutyl phenoxy ethoxy ethyl dimethyl benzyl ammonium chloride mono-hydrate). The use of these and other additives is optional and while contemplated in the commercial practice ofthe invention is not claimed as essential to the anti-perspirant function of the compositions.

In preferred compositions of my invention the concentration of the water-soluble salt of the zirconium or hafnium is from about 3% to about 30% by weight and the concentration-of the basic aluminum compound from about.2% to about-20% by weight, all-on an anhydrous basis. Optimum results are achieved when the atomic ratio of aluminum to zirconium or hafnium is within the range from about 3:1 and-2:1 and when the concentration of zirconium or hafnium salt-is from about 4% to about 20%; and the concentration of the basic aluminum compound is from about 4% to about 15%, all concentrations being expressed by weight on an anhydrous basis. In all cases, however, the proportions of all the constituents of my cosmetic preparations should be so related that the pH of the composition is in the range from about 3 to about 5 and preferably in the range from about3.5 to about 4.5.

The anti-perspirant compositions. of, my invention are characterized by a pH which rises to an equilibriumvalue as the composition ages. I have foundthat the equilibrium pH value is normally reached within about one.

weeks time. Thus, an. anti-perspirant solution comprising 8.0% zirconyl chloride octahydrate, 7.0% aluminum chlorhydroxide complex, 12.0% glycine and;73.0%.water had a pH of 3.9 after; aging for 24 hours .and on further aging reached anv equilibrium pH of 4.3., An anti.- perspirant solution comprising 8.0% zirconyl chloride octahydrate, 7.()%- aluminum chlorhydroxide complex, 2.5% glycine and 82.5% water exhibited a pH of 3.4 after 24 hoursv and reached an equilibrium pH of 3.8. The pH of these solutions immediately after preparation was probably. slightly lower than the pH value after the 24 aging hour period but such small change as might be expected inthat length of time is of little consequence. In fact, the pH values to be given consideration on a practical basis would be the equilibrium pH values and wherever herein pH values are given for any compositions, the values have been determined after the particular compositions have reached an equilibrium pH.

In the following examples, which are by way of illustration only, the efficacy of the various anti-perspirant compounds was determined as follows.

The backs of human subjects were washed with soap and water and a number of cotton disks, about 1 /2 inches in diameter, were placed on the back. Each disk was then saturated with a solution of the anti-perspirant to be tested. The saturated patches were left in place for five minutes, then removed and each test area was blotted. dry with a towel.

After six hours the back was coated with an indicating cream made up of sodium carbonate, phenolphthalein and an oleaginousbase, and the subject was exposed toan environment of heat and high humidity to induce sweating. This indicating cream turns a bright red wherever a droplet. of perspiration appears. Thus, in areas where effective anti-perspirants had been applied only a few drops of perspiration appeared, the resultant 6 few bright red droplets, contrasting. these areas with: the surrounding untreated areas, which showed. a igh. pro portion of the red droplets.

After the sweat pattern was fully developed a photograph of the subjects back was made. 8 x. 10 inch prints of these photographs were obtained so that the test areas on the prints were about one inch in diameter. The number of sweat droplets appearing in a square one-half inch on a side were counted on each test area and a count of the number of sweat droplets in an equal-sized but untreated area was also made. The percentage reduction in, sweating was then determined by a comparison of the count for the untreated area with the count for a treated area.

Example 1.Pour anti-perspirant solutions having the following approximate compositions were prepared:

These. solutionswhen tested for anti-perspirant eificacy accordingto the foregoingmethod gave-the results app ering in. the table below.

Number Average Solution of pH Percent subjects reduction in sweating A 12 3. 75. 2 B 9 4. 03 66. 5 C l5 4. 30 63. 1 D 4 4. 25 66; 3

These data maybe compared with the resultsobtained' from testing a 20% solution of aluminum chloride, which is generally accepted as being an eifective anti-perspirant, and which gave a solution pH of 2.3 and an average percent reduction in sweating of 61.2% when applied to fifteen. subjects.

It is readily apparent from the above that the anti:- perspirant preparations of my invention, .whereinthe anti-perspirant ingredients are presentin the preferred amounts heretofore specified, are greatly superior in effectiveness even. when.v compared with a material which isv considered. to. be the best anti-perspirant astringent known.

Although, ashasbeen hereinbefore pointed out, high concentrations; of amino acid have a deleterious. eifect on anti-perspirant efficacy, it isalso apparent from the above that even with amino acid concentration as high as 12%,- the efilcacy of the amino acid-containing composition is still superior to that of the 20% aluminum chloride solution.

Moreover, the higher pH of the anti-perspirant compositions of myinvention would render them less irritating to the skin andless damaging to clothing.

Example v2.F.or comparison purposes, anti-perspirant: efiicacy determinations were made. according ,to the fore going method for 10% solutions of zirconyl chloride octahydrate (unbufiered), aluminum chloride (unbufiered) and aluminum chlorhydroxide with the following results.

It is apparent from the above data. that the zirconyl compound is a highly effective anti-perspirant although its high acidity makes it impractical of use.

A comparison of the pH and percent reduction in sweating .values for zirconyl chloride octahydrate in Example 2 with the corresponding values of solution A, B and D in Example 1 will clearly show that the compositions of my invention offer a practical solution to the problem of controlling the acidity of zirconium and hafnium salts while at the same time preserving their eifective anti-perspirant action.

Example 3.A series of determinations was made, according to the hereinbefore described method, of the anti-perspirant efficacy of 10% solutions of the materials listed in the table below with the indicated results.

Here again, a comparison of the pH and percent reduction in sweating values for the zirconyl compounds in the table above with corresponding values of Solutions A, B, and D in Example 1 clearly indicate that the compositions of my invention offer a practical solution to the problem of controlling the acidity of the zirconyl salts while at the same time preserving their high anti-perspirant effectiveness.

Example 4.That the zirconium salts of weak acids are ineffective anti-perspirants and thus offer no solution to the problem of high acidity in eifective zirconiumcontaining anti-perspirant preparations is adequately supported by the following data. All determinations were made on 5 subjects with solutions of the material according to the above described method.

Example 5.--A series of tests were made to determine the effect of various anti-perspirants on the tensile strength of textiles. The procedure was as follows;

Cotton muslin was washed, rinsed thoroughly and ironed dry. It was then cut into strips measuring 6 inches by 21 inches. An area one inch wide was marked down the center of each strip and the area was saturated with the anti-perspirant to be tested. An identical strip containing non anti-perspirant was carried through the treatment along with the anti'perspirant-containing strips to serve as a control. All strips were stored for 24 hours at 70 F. and 70% relative humidity, were then ironed at 275 F. and again stored under the same conditions for three hours. At the end of this period the strips were tested for tensile strength using a Scott Tensile Strength Machine with one inch jaws.

Solution A: Percent ZrOCla'8H2O 8.0 Alz(0I-I) sCl-2H2O 7.0 Glycin 2.5 Water" 82.5

Solution B:

ZrOClz- 8H2O 8.0 Al2(OH)5C1'2H2O 7.0 Glycin 5.0 Water 80.0 Solution C:

ZrOClz' 8H2O 8.0 A12 OH) 5C1 2H2O 7.0 Glycine- 12.0 Water 73.0

Cream ZrOClz- 8H2O 9.0 Al2(OH) 5Cl-2H2O 8.0 Glycine 3.0

Lotion ZrOClz SHzO 9.0 Al2(OH) 5Cl-2I-I2O 7.0 Glycine 6.0

1 Also contain various. other ingredients as hereinbefore pointed out.

Average Percent Anti-perspirant pH breaking loss in strength, strength lbs.

Control (none) 47.1

10% ZTOCl2.8H20 0.8 15. 6 66. 0

10% AlOls.6Hz 2.3 2.0 95. 8

15% Alz(0H)sC 4. 2 35. 4 24. 8

S0 ution 3. 8 38. 9 17. 5

Solution 13-. 4.0 43. 9 6. 9

Solution 4. 8 50.0 0.0

Cream 4. 0 39. l 17. l

Lotion 42. 2 10. 4

It is apparent from the above data that the anti-pen spirant compositions of my invention would be very advantageous of use from the standpoint of fabric damage.

It is to be appreciated the corresponding anti-perspirant compositions containing a hafnium salt as one of the active ingredients behave in like manner as the zirconium containing compositions and hafnium salts may be substituted for the zirconium salts in any of the examples contained herein, and the chlorides, bromides, iodides, and nitrates may be used interchangeably, with comparable results.

Having thus described my invention, I claim:

1. An aqueous perspiration inhibiting composition comprising (l) a stable Water-soluble salt of a group IVB metal selected from the group consisting of hafnium and zirconium and mixtures of these and a monobasic mineral acid the anion of which is a radical selected from the group consisting of Cl, I, Br, and N03, (2) a basic aluminum compound of the approximate general empirical formula Al2(OH)e nXn where X is a monovalent acid anion selected from the group consisting of Cl, I", Brand NOT and n has an average value from about 0.8 to about 2, and (3) an amino acid, in which the number of amino groups is equal to the number of carboxyl groups in the molecule, in an amount at least about 1% by weight of the composition, on an anhydrous basis, and sufficient to prevent gelling of the composition, the water in the composition being from about 25 to by weight, the concentration of constituents (1) and (2) being from about 5% to about 50% by weight, on an anhydrous basis, and the proportions of said constituents (l) and (2) being so related that the atomic ratio of aluminum to the group lVB metal in the composition is between about 3.5:1 and 15:1.

2. The composition of claim 1 wherein the concentration of the Water-soluble salt of the group IVB metal is from about 3% to about 30% by weight, and the concentration of the basic aluminum compound is from about 2% to about 20% by weight, the concentration in all cases being on an anhydrous basis.

3. The composition of claim 2 wherein the concentrations of the water-soluble salt of the group IVB metal, the basic aluminum compound and the amino acid are such that the said constituents are completely in solution in the composition.

4. The composition of claim 2 wherein the amino acid is from about 1% to about 5% by weight on an anhydrous basis.

5. The composition of claim 4 wherein the amino acid is glycine.

6. The composition of claim 4 wherein the atomic ratio of aluminum to the group IVB metal is between about 3 :1 and 2:1.

7. The composition of claim 6 wherein the concentration of the water-soluble salt of the group IVB metal is from about 4% to about 20% by weight on an anhydrous basis.

8. The composition of claim 7 wherein the concentration of the basic aluminum compound is from about 4% to about 15% by weight on an anhydrous basis.

9. The composition of claim 8 wherein the anion group of the water-soluble salt of the group IVB metal is Cl and the monovalent acid anion of the basic aluminum compound is Cl".

10. An aqueous perspiration inhibiting composition comprising (1) zinconyl chloride octahydrate, (2) a basic aluminum compound of the approximate general empirical formula Al2(OH)6-7I.Xn, where X is a monovalent acid anion selected from the group consisting of C1", B1", 1-, N031 and n has an average value of about 0.8 to about 2, and (3) glycine, in an amount at least about 1% by weight of the composition, on an anhydrous basis, and sufficient to prevent gelling of the composition, the Water in the composition being from about 25% to 90% by Weight, the concentration of constituents (l) and (2) together being from about 5% to about by Weight, on an anhydrous basis, and the proportions of said constituents (1) and (2) being so related that the atomic ratio of aluminum to zirconium in the composition is between about 3.521 and 15:1.

References (Cited in the file of this patent UNITED STATES PATENTS 2,118,566 Miles May 24, 1933 2,236,387 Wallace Mar. 25, 1941 2,492,085 Andersen oee'zo, 1949 2,734,848 Berger Feb. 14, 1956 OTHER REFERENCES Hilfer: Drug and Cosmetic Ind., February 1950, pp. 154,155 and 238.

Am. Perfume: and Ess. Oil Review, vol. 5 8, November 1951, p. 335.

Merck Index, 6th ed. (1952), p. 1025.

Schimmel Briefs, Schimmel and Co. Inc., l W. 26th St., New York City, No. 206, May 1952 (1 page). 

1. AN AQUEOUS PERSPIRATION INHIBITING COMPOSITION COMPRISING (1) A STABLE WATER-SOLUBLE SALT OF A GROUP IVB METAL SELECTED FROM THE GROUP CONSISTING OF HAFNIUM AND ZIRCONIUM AND MIXTURES OF THESE AND A MONOBASIC MINERAL ACID THE ANION OF WHICH IS A RADICAL SELECTED FROM THE GROUP CONSISTING OF CI, I, BR, AND NO3, (2) A BASIC ALUMINUM COMPOSITING OF THE APPROXIMATE GENERAL EMPIRICAL FORMULA AL2(OH)6-NXN WHERE X IS A MONOVALENT ACID ANION SELECTED FROM THE GROUP CONSISTING OF CI-,I-,BR-AND NO3- AND N HAS AN AVARGE VALUE FROM ABOUT 0.8 TO ABOUT 2, AND (3) AN AMINO ACID, IN WHICH THE NUMBER OF AMINO GROUPS IS EQUAL TO THE NUMBER OF CARBOXYL GROUPS IN THE MOLECULE, IN AN AMOUNT AT LEAST ABOUT 1% BY WEIGHT OF THE COMPOSITION, ON AN ANHYDOUS BASIS, AND SUFFICIENT TO PREVENT GELLING OF THE COMPOSITON, THE WATER IN THE COMPOSITION BEING FROM ABOUT 25 TO 90% BY WEIGHT, THE CONCENTRATION OF CONSITITUENTS (1) AND (2) BEING FROM ABOUT 5% TO ABOUT 50% BY WEIGHT, ON AN ANHYDROUS BASIS, AND THE PROPORTIONS OF SAID CONSTITUENTS (1) AND (2) BEING SO RELATED THAT THE ATOMIC RATIO FOR ALUMINUM TO THE GROIP IVB METAL IN THE COMPOSITION IS BETWEEN ABOUT 3.5:1 AND 1.5:1. 